The reaction of sodium perfluoroalkanesufinates with coumarin in the presence of Mn(Oac)=3.2H=2O was studied. Sodium perfluoroalkanesufinates, R=FSO=2Na[R=FF(CF=2)=6, 2a; F(CF=2)=7, 2b; F(CF=2)=8, 2c; Cl(CE=2)=4, 2d; Cl(CF=2)=6, 2e] reacted readily with a small excess of coumarin to give the corresponding 3-perfluoroalkylated coumarins (3a-e), while poly-perfluoroalkylation of coumarin occurred when excess 2 was used in the reaction, and 3,6-diperfluoroalkylcoumarins (4) and 3,6,8-triperfluoroalkylcoumarins (5) were isolated as major products according to the ratio of starting materials.